Production of halogeno fatty acid esters



Patented Oct. 13, 1953 PRODUCTION OF HALOGENO FATTY ACID ESTERS Elbert C. Ladd, Passaic, N. J., and Herbert Sargent, San Anselmo, Calif., assignors to United States Rubber Company, New York, N. Y., a corporation of New Jersey No Drawing. Application October 6, 1950, Serial No. 188,872

1 Claim. (Cl. 260-408) This invention relates to a novel method for the synthesis of certain halogeno fatty acid esters.

More particularly, the invention relates to the discovery that certain esters of certain polyhalogeno fatty acids containing halogen in the alpha position and halogen in at least one other Examples of the invention include the following:

Starting material:

CICH2CH2CCI2COOC2H5 CH3CHC1CHzCCl2COOC2H5 CH2BrCH2CBr CH3) COOCzHs position can be selectively hydrogenated so as c c ccl cooc l-k to replace by hydrogen the halogen in the alpha (C1CH2CH2)2CC1COOC2H5 p l l n nly. CH2BrCH2CCl(CI-I3)COOC2Hs The invention relates to hydrogenation of fatty esters of the type CH2CICHBICH2CHBICOOC2H5 CH3 CHCICCI COOCzHs) CHzCHCl (CH2)sH x Product:

| C1CH2CH2CHC1COOC2H5 CHaCHClCHzCI-ICICOOCzHe R CI-IzBI'CHzCH CH3) COOCzHs CH'3CH2CHC1COOC2H5 which produces esters of the type CHzClCHBrCHzCHzCOOCzHs CHaCHC1CH(COOC2H5)2CH2CHCl (CH2) 6H Where X represents chlorine or bromine; A is The products are useful as plasticizers, and as allienylene; R represents X, hydrogen, alkyl, intermediates for the preparation of certain or haloalkyl; and R is lower alkyl. Examples amino acids, such as lysine and as intermediates of such alkyl and haloalkyl radicals are methyl, for the preparation of certain lactones, g ethyl: propyl, butyl, almyly heptyl, 0013371, gamma-undecalactone (the so-called peach nonyl, decyl, undecyl, dodecyl tridecyl, tetraaldehyde) useful as perfumes or perfume bases. d cyl, d y cy Chloromethyl, beta- The following examples illustrate the invention chloroethyl, beta-chloropropyl, beta-chlorobutyl, 39 i m d t il betachloroamyl, beta-chlorohexyl, beta-chloroheptyl, beta-chlorooctyl, beta-chlorononyl, betachlorodecyl, beta-chloroundecyl, beta-chlorododeoyl, beta-chlorotridecyl, beta-chlorotetradecyl, beta chlorohexadecyl, beta chloroheptadecyl, beta-chlorocctadecyl, beta-bromoethyl, beta-bromopropyl beta bromobutyl beta'bmmoamyl' ence of a free-radical type reaction initiator e betabromohexyl' beta'mmmoheptyl' beta'bromo' an acyl peroxide such as benzoyl peroxide. Eth yl octyl, beta-bromononyl, beta-bromodecyl, beta 40 a1pha chloro gamma bromobutymte (2295 g) bromwndecyl, beia-bromododecfli is added to 35 ml. or ethyl alcohol, the latter tridecyl, beta-bromotetradecyl, beta-bromohexcontaining 15 gm of Dre-reduced platinum decy 'b t pfi beta-bromooctaoxide and also containing 0.12 mole of ammonia. decyl. gamma-chlorobutyl, a b b ty The mixture is enclosed in a vessel connected to etc. a source of hydrogen at atmospheric pressure Example I A starting material, ethyl alpha-chloro-gamma-bromobutyrate, is prepared by reacting ethyl bromochloroacetate with ethylene in the pres- 3 The vessel is vogorously agitated during the absorption of hydrogen. At the end of 1 hours 2500 ml. of H2 have been absorbed and absorption has ceased. The reaction mixture is diluted with about three volumes of water and extracted with petroleum ether. The extract is dried over sodium sulfate and then subjected to fractional distillation to yield 11 gms. of ethyl gamma-bromobutyrate having a boiling point of 'I3-'I4.5 C./7 mm.

Percent bromine found, 43.67 Theory,

Example II To a solution of 2.0 gms. of potassium cyanide in absolute ethanol are added 1.9 gms. of the product of Example I. The mixture is heated on a steam bath, whereupon the precipitation of inorganic salt is soon apparent. After being heated for four hours the mixture is diluted with water and extracted twice with a solvent consisting of two parts of ethyl alcohol and one part of petroleum ether. The extract is concentrated by heating, to produce a syrup which is considered to be ethyl gamma-cyanobutyrate. This syrup is heated on a steam bath with 20 ml. 12-N hydrochloric acid for 2 /4 hours, then diluted with water and extracted twice with ether. The ether extract is dried over sodium sulfate and then concentrated by heating, to obtain a semi-crystalline residue. The semicrystalline residue is crystallized three times from isopropyl alcohol to yield glutaric acid, M. P. 95-95.2 C. This example proves the overall sequence of reactions to be:

and about 25 C.

free radicals CHBrClC OO C1H5 CHF-C H2 H2 CHzBl'CHzCHClC O Calls potassium cyanide ysis CH2CNCH2CH2C O O C2115 HOOCCHIGHflCHiOOOH Example III (a) Ethyl alpha, alpha, gamma-trichlorobutyrate (prepared by reacting one mole of ethylene and one mole of ethyl trichloroacetate in the presence of free radicals) is reduced by dissolving 44 gms. thereof in 100 ml. ethanol and mixing (b) Experiment III(a) is repeated except for .the following variations: 0.2 mole of-ammonia is added at the start of the reaction. It is soon observed that hydrogen absorption is slow. Therefore, 12 ml. of glacial acetic acid are added and the reaction is resumed. At the end of one hour 4330 ml. of hydrogen have been absorbed and reaction has virtually ceased. The reaction mixture is diluted with water and extracted with petroleum ether and the extract dried over sodium sulfate The extracts from (a) and (b) are combined and fractionally distilled to yield 57 gms. of ethyl alpha, gamma-dichlorobutyrate, B. P., 7243 C./3 mm.

Percent chlorine (Calc. for

CHzClCHzCHClCOOCzHs) 38.34; percent chlorine found, 39.29.

Example IV Ethyl 2,2,6-trichlorohexanoate (prepared by reacting one mole of ethyl trichloroacetate with two moles of ethylene in the presence of free radicals) is reduced by dissolving 74.3 gms. thereof in ml. of absolute ethanol containing 0.3 mole of ammonia and 25 ml. of glacial acetic acid, adding .4 gm. of prereduced platinum oxide in 10 ml. ethanol, and treating with hydrogen as in Example I until 6000 ml. are absorbed. This requires about 1 /2 hours. The reaction mixture is then diluted with water, extracted with petroleum ether and the extract is dried over sodium sulfate. The extract is distilled to yield 56 gms. of ethyl alpha-omega-dichlorohexanoate having a B. P. of 102-104 C./3 mm.

Percent chlorine (theory), 33.45; percent chlorine found, 33.08.

' Example V Ethyl 2,2,4-trichlorodecanoate is reduced by dissolving 30.25 parts thereof in 48 parts of ethanol and admixing with it a suspension of approximately 0.3 part of platinum oxide in 7.8 parts of ethanol which has been previously treated with hydrogen until absorption ceases. The mixture is then enclosed in a vessel connected to a source of hydrogen at atmospheric pressure and about 25 C. At the end of 1 hour the reaction is interrupted while a solution of 0.51 part of ammonia in 6.2 parts of ethanol is added. The reaction is then resumed and at the end of an additional hour the absorption of hydrogen virtually ceases, a total of 0.122 part of hydrogen having been absorbed.

The reaction mixture is then diluted with 3 volumes of water and extracted with several portions of petroleum ether (a commercial mixture of aliphatic hydrocarbons comprising mostly pentane, hexane and heptane). The extract is dried and fractionally distilled to yield 19 parts of the new compound, ethyl 2,4-dichlorodecanoate, B. l18-120 C./2 mm. Upon treatment with alcoholic ammonia the ester is converted to the corresponding 2,4-dichlorodecanoamide, which melts at 95.596.0 C. after recrystallization from petroleum ether.

Example VI bromodecanoate having a B. P. of 99-101 C./1 mm.

Example VII Thirteen and five tenths gms. of ethyl 2,2-dichlorodecanoate (13.5 g.) is dissolved in 50 ml. of ethanol containing 1.3 gms. of prereduced platinum oxide. The mixture is then treated with hydrogen as in Example I until 1,300 ml. are

absorbed. The reaction mixture i then diluted with water, extracted with petroleum ether. The ether extract is dried and fractionally distilled to yield 7 gms. of crude ethyl 2-chlorodecanoate boiling at 104108 C./2 mm.

Having thus described our invention, what we claim and desire to protect by Letters Patent is:

A method of forming fatty esters of the formula from fatty esters of the formula X-A-C-C o o R References Cited in the file of this patent UNITED STATES PATENTS Name Date Ladd et a1 July 18, 1950 Number 

